Silver adlayer can be formed on Au single crystal surfaces by surface-induced dissociation of Ag coordinated complex precursor [(dPtaP-Ag)(2)](NO3)(2), where dptap denotes 2-(2-pyridylimino)-2H-1,2,4-thia-diazolo [2,3-a] pyridine, by immersing in the acetonitrile containing such a complex. STM study shows (4 x 4) and (root2 x 5root2) adlayer structures on Au(111) and Au(100), respectively, resembling the Ag UPD adlayer structures on the corresponding Au single crystal electrodes at high underpotential shifts. The formation of the Ag adlayer is confirmed by XPS study, and computational calculations suggest a mechanism of surface-induced weakening and dissociation of the (electrostatic) Ag-N bond by charge transfer from the Au surface. (C) 2004 Elsevier B.V. All rights reserved.